Fungicidal phenylamidine derivatives

ABSTRACT

The invention provides fungicidal compounds of formula I and salts thereof:  
                 
 
     wherein  
     the various radicals and substituents are as defined in the description, fungicidal compositions containing them and method for combating fungi which comprises applying these.

[0001] This invention relates to new fungicidal phenylamidinederivatives, their process of preparation and the fungicidalcompositions containing them.

[0002] WO 95/22532 relates to substituted phenyltriazolinones claimed asherbicides and discloses inter alia a compound of formula A for whichthere is no characterising data therein.

[0003] The abstract, composition claim and use claim refer only to theuse of such compounds as herbicides and indeed the description supportsthe invention only with herbicidal activity data. There is a sentence inthe specification that states that certain compounds show fungicidalactivity, although no fungicidal activity data are provided. Noindication is given as to which compounds are fungicidal and there is nosuggestion that compound A could be fungicidal.

[0004] We have now found that certain phenylamidines have fungicidalactivity. Therefore, the invention provides the use of a compound ofgeneral formula (I) and salts thereof as fungicides:

[0005] wherein

[0006] R¹ is chosen from among alkyl, alkenyl, alkynyl, acyl,carbocyclyl, heterocyclyl, each of which may be substituted, cyano andhydrogen;

[0007] R² and R³, which may be the same or different, are any groupdefined for R¹; cyano; acyl; —OR^(a), —NR^(a)R^(b) or —SR^(a), whereR^(a) and R^(b), which may be the same or different, are chosen fromalkyl, alkenyl, alkynyl, acyl, carbocyclyl, heterocyclyl, each of whichmay be substituted, and cyano; or

[0008] R² and R³, or R² and R¹, together with their interconnectingatoms may form a ring, which may be substituted;

[0009] R⁴ is chosen from among alkyl, alkenyl, alkynyl, carbocyclyl,heterocyclyl, each of which may be substituted; hydroxy; mercapto;azido; nitro; halogen; cyano; acyl; optionally substituted amino;cyanato; thiocyanato; —SF₅; —OR^(a); —SR^(a) and —Si(R^(a))₃, where Rais alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of whichmay be substituted;

[0010] m is 0 to 3;

[0011] when present R⁵, which may be the same or different to any otherR⁵, is any group defined for R⁴;

[0012] R⁶ is optionally substituted carbo- or hetero-cyclyl; and

[0013] A is a direct bond, —O—, —S(O)_(n)—, —NR⁹—, —CR⁷═CR⁷—, —C≡C—,—A¹—, —A¹—A¹—, —O—(A¹)_(k)—O—, —O—(A¹)_(k)—, —A³—, —A⁴—, —A¹O—,—A¹S(O)_(n)—, —A²—, —OA²—, —NR⁹A²—, —OA²—A¹—, —OA²—C(R⁷) ═C(R⁸)—,—S(O)_(n)A¹—, —A¹—A⁴—, —A¹—A⁴—C(R⁸)═N—N═CR⁸—, —A¹—A⁴—C(R⁸)═N—X²—X³—,—A¹—A⁴—A³—, —A¹—A⁴—N(R⁹)—, —A¹—A⁴—X—CH₂—, A¹—A⁴—A¹—, —A¹—A⁴—CH₂X—,—A¹—A⁴—C(R⁸)═N—X²—X³—X¹—, —A¹—X—C(R⁸)═N—,—A¹—X—C(R⁸)═N—N═CR⁸—A¹—X—C(R⁸)═N—N(R⁹)—, —A¹—X—A²—X¹—, —A¹—O—A³—,—A¹—O—C(R⁷)═C(R⁸)—, —A¹—O—N(R⁹)—A²—N(R⁹)—, —A¹—O—N(R⁹)—A²—,—A¹—N(R⁹)—A²—N(R⁹)—, —A¹—N(R⁹)—A²—, —A¹—N (R⁹)—N═C(R⁸)—, —A³—A¹—,—A⁴—A³—, —A²—NR⁹—, —A¹—A²—X¹—, —A¹—A¹—A²—X¹—, —O—A²—N(R⁹)—A²—,—CR⁷═CR⁷—A²—X¹—, —C═C—A²—X¹—, —N═C(R⁸)—A²—X¹—, —C(R⁸)═N—N═C(R⁸)—,—C(R⁸)═N—N(R⁹)—, —(CH₂)₂—O—N═C(R⁸)—ou—X—A²—N(R⁹)—

[0014] where:

[0015] n is 0, 1 or 2,

[0016] k is 1 to 9,

[0017] A¹ is —CHR⁷—,

[0018] A² is —C(═X)—,

[0019] A³ is —C(R⁸)═N—O—,

[0020] A⁴ is —O—N═C(R⁸)—,

[0021] X is O or S,

[0022] X¹ is O, S, NR⁹ or a direct bond,

[0023] X² is O, NR⁹ or a direct bond,

[0024] X³ is hydrogen, —C(═O)—, —SO₂— or a direct bond,

[0025] R⁷, which may be the same or different to any other R⁷, is alkyl,alkenyl, alkynyl, cyano, acyl, hydroxy, alkoxy, haloalkoxy, alkylthio,cycloalkyl or phenyl, each of which may be substituted; or is hydrogenor halogen;

[0026] R⁸, which may be the same or different to any other R⁸, is alkyl,alkenyl, alkynyl, alkoxy, alkylthio, carbo- or hetero-cyclyl, each ofwhich may be substituted; or is hydrogen;

[0027] R⁹, which may be the same or different to any other R⁹, isoptionally substituted alkyl, optionally substituted carbo- orhetero-cyclyl, hydrogen or acyl; or two R⁹ groups on A, together withthe connecting atoms, form a 5 to 7 membered ring;

[0028] where the moiety depicted on the right side of linkage A isattached to R⁶;

[0029] or —A—R⁶ and R⁵ together with benzene ring M form an optionallysubstituted fused ring system.

[0030] Preferably R¹ is alkyl, alkenyl, alkynyl or acyl, each of whichmay be substituted by alkoxy, haloalkoxy, alkylthio, halogen oroptionally substituted phenyl (preferably phenyl optionally substitutedby alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio, each containing 1to 5 carbon atoms, or halogen), or is cyano or hydrogen. R¹ isespecially C₁-C₁₀ alkyl (e.g. methyl) or hydrogen.

[0031] Preferably R² and R³, which may be the same or different, arealkyl, alkenyl or alkynyl, each of which may be substituted by alkoxy,haloalkoxy, alkylthio, halogen or optionally substituted phenyl(preferably phenyl, optionally substituted by alkyl, haloalkyl, alkoxy,haloalkoxy or alkylthio, each containing 1 to 5 carbon atoms, or byhalogen), or is hydrogen or alkycarbonyl. R² and R³, which may be thesame or different, are especially C₁-C₁₀ alkyl (e.g. methyl or ethyl) orhydrogen.

[0032] Preferably R⁴ is alkyl, alkenyl, or alkynyl, each of which may besubstituted by alkoxy, haloalkoxy, alkylthio, halogen or optionallysubstituted phenyl (preferably phenyl optionally substituted by alkyl,haloalkyl, alkoxy, haloalkoxy or alkylthio, each containing 1 to 5carbon atoms, or halogen); or is hydroxy; halogen; cyano; acyl(preferably —C(═O)R^(c), —C(═S)R^(c) or —S(O)_(p)R^(c), where R^(c) isalkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, amino, monoalkylamino,dialkylamino or phenyl optionally substituted by alkyl, haloalkyl,alkoxy, haloalkoxy or alkylthio; phenyloxy, phenylthio, carbocyclyl,heterocyclyl); alkoxy; haloalkoxy; or alkylthio. R⁴ is especially C₁-C₁₀alkyl (e.g. methyl or ethyl) or halogen.

[0033] Preferably m is 0 or 1, especially 1.

[0034] When present, R⁵ is preferably a group defined for preferred R⁴above. R⁵ is especially C₁-C₁₀ alkyl or halogen.

[0035] When present, the group R⁵ is preferably attached at the 5position of ring M.

[0036] Preferably A is a direct bond, —O—, —S(O)_(n)A¹—, —O(A¹)_(k)—,—S(O)_(n)—, —NR⁹A²—, —A²—, —OA²—, —OA²—A¹—, —NR⁹— or —O(A¹)_(k)O—.Particularly A is a direct bond, —O—, —S—, —NR⁹—, —CHR⁷— or —O —CHR⁷—.Especially A is a direct bond or —O—.

[0037] When present, R⁹ is alkyl, alkenyl, or alkynyl, each of which maybe substituted by alkoxy, haloalkoxy, alkylthio, halogen or optionallysubstituted phenyl (preferably phenyl optionally substituted by alkyl,haloalkyl, alkoxy, haloalkoxy or alkylthio, each containing 1 to 5carbon atoms, or halogen); or is hydrogen (R⁹ is especially C₁-C₁₀ alkylor hydrogen).

[0038] When present, R⁷ is alkyl, alkenyl, or alkynyl, each of which maybe substituted by alkoxy, haloalkoxy, alkylthio, halogen or optionallysubstituted phenyl (preferably phenyl optionally substituted by alkyl,haloalkyl, alkoxy, haloalkoxy or alkylthio, each containing 1 to 5carbon atoms, or by halogen); or is hydroxy; halogen; cyano; acyl;alkoxy; haloalkoxy; alkylthio; or hydrogen (R⁷ is especially C₁-C₁₀alkyl or hydrogen).

[0039] Preferably A is attached to the 4 position of benzene ring M.

[0040] Preferably R⁶ is optionally substituted phenyl or optionallysubstituted aromatic heterocyclyl [preferably thiazolyl, isothiazolyl,thiadiazolyl (particularly 1,2,4-thiadiazolyl), pyridyl or pyrimidinyl].

[0041] When substituted, R⁶ may be substituted by one or moresubstituents, which may be the same or different, and may be selectedfrom the preferred list: alkyl, alkenyl, alkynyl, carbo- orheterocyclyl, each of which may be substituted; hydroxy; mercapto;azido; nitro; halogen; cyano; acyl; optionally substituted amino;cyanato; thiocyanato; —SF₅; —OR^(a); —SR^(a) and —Si(R^(a))₃, whereR^(a) is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each ofwhich may be substituted.

[0042] A preferred list of substituents on R⁶ is: hydroxy; halogen;cyano; acyl (preferably —C(═O)R^(c), —C(═S)R^(c) or —S(O)_(p)R^(c),where R^(c) is alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, amino,monalkylamino, dialkylamino or phenyl optionally substituted by alkyl,haloalkyl, alkoxy, haloalkoxy or alkylthio, phenyloxy, phenylthio,carbocyclyl, heterocyclyl); amino; alkylamino; dialkylamino; alkyl;haloalkyl; RaO-alkyl; acyloxyalkyl; cyano-oxyalkyl; alkoxy; haloalkoxy;alkylthio;

[0043] carbocyclyl (preferably cyclohexyl or cyclopentyl) optionallysubstituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio; andbenzyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy oralkylthio.

[0044] In a preferred embodiment, the invention provides the use of acompound of general formula (I) and salts thereof as fungicides wherein:

[0045] R¹ is alkyl, alkenyl or alkynyl, each of which may be substitutedby alkoxy, haloalkoxy, alkylthio, halogen or phenyl optionallysubstituted by alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio orhalogen; or is hydrogen;

[0046] R² and R³, which may be the same or different, are as defined forR¹ in this embodiment, or are alkoxy, alkoxyalkoxy, benzyloxy, cyano oralkylcarbonyl;

[0047] R⁴ is alkyl, alkenyl or alkynyl, each of which may be substitutedby alkoxy, haloalkoxy, alkylthio, halogen or phenyl optionallysubstituted by alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio orhalogen; or is hydroxy; halogen; cyano; acyl (preferably —C(═O)R^(c),—C(═S)R^(c) or —S(O)_(p)R^(c), where R^(c) is alkyl, haloalkyl, alkoxy,haloalkoxy, alkylthio, amino, monoalkylamino, dialkylamino or phenyloptionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy oralkylthio; phenyloxy, phenylthio, carbocyclyl, heterocyclyl);

[0048] m is 0 or 1;

[0049] when present, R⁵ is a group defined for R⁴ in this embodiment;

[0050] A is a direct bond, —O—, —S—, —NR⁹—, —CHR⁷— or —O—CHR⁷—,

[0051] wherein when present, R⁹ is alkyl, alkenyl, or alkynyl, each ofwhich may be substituted by alkoxy, haloalkoxy, alkylthio, halogen orphenyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy,alkylthio, or halogen; or is hydrogen; and R⁷ is a group defined for R⁹in this embodiment, or is hydroxy; halogen; cyano; acyl; alkoxy;haloalkoxy or alkylthio;

[0052] A is attached to the 4 position of benzene ring M; and

[0053] R⁶ is phenyl or aromatic heterocyclyl, optionally substituted byone or more substituents, which may be the same or different, and may beselected from the list: hydroxy; halogen; cyano; acyl (preferably—C(═O)R^(c), —C(═S)R^(c) or —S(O)_(p)R^(c), where R^(c) is alkyl,haloalkyl, alkoxy, haloalkoxy, alkylthio, amino, monoalkylamino,dialkylamino or phenyl optionally substituted by alkyl, haloalkyl,alkoxy, haloalkoxy or alkylthio; or phenyloxy, phenylthio, carbocyclyl,heterocyclyl); amino; alkylamino; dialkylamino; alkyl; haloalkyl;R^(a)O-alkyl; acyloxyalkyl; cyano-oxyalkyl; alkoxy; haloalkoxy;alkylthio; carbocyclyl (preferably cyclohexyl or cyclopentyl) optionallysubstituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio; andbenzyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy oralkylthio.

[0054] Any alkyl group may be straight or branched and is preferably of1 to 10 carbon atoms, especially 1 to 7 and particularly 1 to 5 carbonatoms.

[0055] Any alkenyl or alkynyl group may be straight or branched and ispreferably of 2 to 7 carbon atoms and may contain up to 3 double ortriple bonds which may be conjugated, for example vinyl, allyl,butadienyl or propargyl.

[0056] Any carbocyclyl group may be saturated, unsaturated or aromatic,and contain 3 to 8 ring-atoms. Preferred saturated carbocyclyl groupsare cyclopropyl, cyclopentyl or cyclohexyl. Preferred unsaturatedcarbocyclyl groups contain up to 3 double bonds. A preferred aromaticcarbocyclyl group is phenyl. The term carbocylic should be similarlyconstrued. In addition, the term carbocyclyl includes any fusedcombination of carbocyclyl groups, for example naphthyl, phenanthryl,indanyl and indenyl.

[0057] Any heterocyclyl group may be saturated, unsaturated or aromatic,and contain 3 to 7 ring-atoms up to 4 of which may be hetero-atoms suchas nitrogen, oxygen and sulphur. Examples of heterocyclyl groups arefuryl, thienyl, pyrrolyl, pyrrolinyl, pyrrolidinyl, imidazolyl,dioxolanyl, oxazolyl, thiazolyl, imidazolyl, imidazolinyl,imidazolidinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, isoxazolyl,isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, pyranyl, pyridyl(and pyridyl N-oxide), piperidinyl, dioxanyl, morpholino, dithianyl,thiomorpholino, pyridazinyl, pyrimidinyl, pyrazinyl, piperazinyl,sulpholanyl, tetrazolyl, triazinyl, azepinyl, oxazepinyl, thiazepinyl,diazepinyl and thiazolinyl.

[0058] In addition, the term heterocyclyl includes fused heterocyclylgroups, for example benzimidazolyl, benzoxazolyl, imidazopyridinyl,benzoxazinyl, benzothiazinyl, oxazolopyridinyl, benzofuranyl,quinolinyl, quinazolinyl, quinoxalinyl, dihydroquinazolinyl,benzothiazolyl, phthalimido, benzofuranyl, benzodiazepinyl, indolyl andisoindolyl. The term heterocyclic should be similarly construed.

[0059] Any alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl group,when substituted, may be substituted by one or more substituents, whichmay be the same or different, and may be selected from the list:hydroxy; mercapto; azido; nitro; halogen; cyano; acyl; alkoxycarbonyl;optionally substituted aminocarbonyl; optionally substituted amino;optionally substituted ammonio; optionally substituted carbocyclyl;optionally substituted heterocyclyl; cyanato; thiocyanato; —SF₅;—OR^(a); —SR^(a); —SOR^(a); —SO₂R^(a) and —Si(R^(a))₃, where R^(a) isalkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which maybe substituted. In the case of any carbocyclyl or heterocyclyl group thelist includes additionally: alkyl, alkenyl and alkynyl, each of whichmay be substituted. Preferred substituents on any alkyl, alkenyl oralkynyl group are alkoxy, haloalkoxy or alkylthio, each containing 1 to5 carbon atoms; halogen; or optionally substituted phenyl. Preferredsubstituents on any carbocyclyl or heterocyclyl group are alkyl,haloalkyl, alkoxy, haloalkoxy or alkylthio, each containing 1 to 5carbon atoms; halogen; or optionally substituted phenyl.

[0060] In the case of any alkyl group or any unsaturated ring-carbon inany carbocyclyl or heterocyclyl group the list includes a divalent groupsuch as oxo or imino, which may be substituted by optionally substitutedamino, R^(a) or —OR^(a) (where R^(a) is as defined above). Preferredgroups are oxo, imino, alkylimino, oximino, alkyloximino or hydrazono.

[0061] Any amino group, when substituted and where appropriate, may besubstituted by one or two substituents which may be the same ordifferent, selected from the list: optionally substituted alkyl,alkenyl, alkynyl, carbocyclyl, or heterocyclyl, optionally substitutedamino, —OR^(a) (where R^(a) is as defined above) and acyl groups.Alternatively two substituents together with the nitrogen to which theyare attached may form a heterocyclyl group, preferably a 5 to 7-memberedheterocyclyl group, which may be substituted and may contain otherhetero atoms, for example morpholino, thiomorpholino or piperidinyl.

[0062] The term acyl includes the residues of sulphur andphosphorus-containing acids as well as carboxylic acids. Typically theresidues are covered by the general formulae —C(═X^(a))R^(b),—S(O)_(p)R^(b) and —P(═X^(a))(OR^(a))(OR^(a)), where appropriate X^(a)is O or S, R^(b) is as defined for R^(a), —OR^(a), —SR^(a), optionallysubstituted amino or acyl; and p is 1 or 2. Preferred groups are—C(═O)R^(c), —C(═S)R^(c), and —S(O)_(p)R^(c) where R^(c) is alkyl, C₁-C₅alkoxy, C₁-C₅ alkylthio, phenyl, phenyloxy, phenylthio, carbocyclyl,heterocyclyl or amino, each of which may be substituted.

[0063] Complexes of compounds of the invention are usually formed from asalt of formula MAn or MAn₂, in which M is a metal cation, e.g. copper,manganese, cobalt, nickel, iron or zinc and An is an anion, e.g.chloride, nitrate or sulphate.

[0064] In cases where the compounds of the invention comprise a nitrogenatom which may be oxidised, N-oxides of such compounds are also part ofthe invention.

[0065] In cases where the compounds of the invention exist as the E andZ isomers, the invention includes individual isomers as well as mixturesthereof.

[0066] In cases where compounds of the invention exist as tautomericisomers, the invention includes individual tautomers as well as mixturesthereof

[0067] In cases where the compounds of the invention exist as opticalisomers, the invention includes individual isomers as well as mixturesthereof, including the racemic mixture.

[0068] The compounds of the invention have activity as fungicides,especially against fungal diseases of plants, e.g. mildews andparticularly cereal powdery mildew (Erysiphe graminis) and vine downymildew (Plasmopara viticola), rice blast (Pyricularia oryzae), cerealeyespot (Pseudocercosporella herpotrichoides), rice sheath blight(Pellicularia sasakii), grey mould (Botrytis cinerea), damping off(Rhizoctonia solani), wheat brown rust (Puccinia recondita), late tomatoor potato blight (Phytophthora infestans), apple scab (Venturiainaequalis), and glume blotch (Leptosphaeria nodorum). Other fungiagainst which the compounds may be active include other powdery mildews,other rusts, and other general pathogens of Deuteromycete, Ascomycete,Phycomycete and Basidomycete origin.

[0069] The invention thus also provides a method of combating fungi at alocus infested or liable to be infested therewith, which comprisesapplying to the locus a compound of formula I.

[0070] The invention also provides an agricultural compositioncomprising a compound of formula I in admixture with an agriculturallyacceptable diluent or carrier.

[0071] The composition of the invention may of course include more thanone compound of the invention.

[0072] In addition, the composition can comprise one or more additionalactive ingredients, for example compounds known to possess plant-growthregulant, herbicidal, fungicidal, insecticidal, acaricidal,antimicrobial or antibacterial properties. Alternatively the compound ofthe invention can be used in a simultaneous, sequential or alternativeway with the other active ingredient(s).

[0073] The diluent or carrier in the composition of the invention can bea solid or a liquid optionally in association with a surface-activeagent, for example a dispersing agent, emulsifying agent or wettingagent. Suitable surface-active agents include anionic compounds such asa carboxylate, for example a metal carboxylate of a long chain fattyacid; an N-acylsarcosinate; mono- or di-esters of phosphoric acid withfatty alcohol ethoxylates or alkyl phenol ethoxylates or salts of suchesters; fatty alcohol sulphates such as sodium dodecyl sulphate, sodiumoctadecyl sulphate or sodium cetyl sulphate; ethoxylated fatty alcoholsulphates; ethoxylated alkylphenol sulphates; lignin sulphonates;petroleum sulphonates; alkyl-aryl sulphonates such as alkyl-benzenesulphonates or lower alkylnaphthalene sulphonates, e.g.butyl-naphthalene sulphonate; salts of sulphonatednaphthalene-formaldehyde condensates; salts of sulphonatedphenol-formaldehyde condensates; or more complex sulphonates such as theamide sulphonates, e.g. the sulphonated condensation product of oleicacid and N-methyl taurine; the dialkyl sulphosuccinates, e.g. the sodiumsulphonate of dioctyl succinate; acid derivatives of alkyl glycosidesand alkylpolyglycosides materials and their metal salts, e.g. alkylpolyglycoside citrate or tartrate materials; or mono-, di- and tri-alkylesters of citric acid and their metal salts.

[0074] Nonionic agents include condensation products of fatty acidesters, fatty alcohols, fatty acid amides or fatty-alkyl- oralkenyl-substituted phenols with ethylene and/or propylene oxide; fattyesters of polyhydric alcohol ethers, e.g. sorbitan fatty acid esters;condensation products of such esters with ethylene oxide, e.g.polyoxyethylene sorbitan fatty acid esters; alkyl glycosides, alkylpolyglycoside materials; block copolymers of ethylene oxide andpropylene oxide; acetylenic glycols such as2,4,7,9-tetramethyl-5-decyne-4,7-diol, ethoxylated acetylenic glycols;acrylic based graft copolymers; alkoxylated siloxane surfactants; orimidazoline type surfactants, e.g. 1-hydroxyethyl-2-alkylimidazoline.

[0075] Examples of a cationic surface-active agent include, forinstance, an aliphatic mono-, di-, or polyamine as an acetate,naphthenate or oleate; an oxygen-containing amine such as an amineoxide, polyoxyethylene alkylamine or polyoxypropylene alkylamine; anamide-linked amine prepared by the condensation of a carboxylic acidwith a di- or polyamine; or a quaternary ammonium salt.

[0076] The compositions of the invention can take any form known in theart for the formulation of agrochemicals, for example, a solution, anaerosol, a dispersion, an aqueous emulsion, a microemulsion, adispersible concentrate, a dusting powder, a seed dressing, a fumigant,a smoke, a dispersible powder, an emulsifiable concentrate, granules oran impregnated strip. Moreover it can be in a suitable form for directapplication or as a concentrate or primary composition which requiresdilution with a suitable quantity of water or other diluent beforeapplication.

[0077] A dispersible concentrate comprises a compound of the inventiondissolved in one or more water miscible or semi-water miscible solventstogether with one or more surface active and/or polymeric material.Addition of the formulation to water results in the crystalisation ofthe active ingredient, the process being controlled by the surfactantsand/or polymers resulting in a fine dispersion.

[0078] A dusting powder comprises a compound of the invention intimatelymixed and ground with a solid pulverulent diluent, for example, kaolin.

[0079] An emulsifiable concentrate comprises a compound of the inventiondissolved in a water-immiscible solvent which forms an emulsion ormicroemulsion on addition to water in the presence of an emulsifyingagent.

[0080] A granular solid comprises a compound of the invention associatedwith similar diluents to those that may be employed in dusting powders,but the mixture is granulated by known methods. Alternatively itcomprises the active ingredient absorbed or coated on a preformedgranular carrier, for example, Fuller's earth, attapulgite, silica orlimestone grit.

[0081] Wettable powders, granules or grains usually comprise the activeingredient in admixture with suitable surfactants and an inert powderdiluent such as clay or diatomaceous earth.

[0082] Another suitable concentrate is a flowable suspension concentratewhich is formed by grinding the compound with water or other liquid,surfactants and a suspending agent.

[0083] The concentration of the active ingredient in the composition ofthe present invention, as applied to plants is preferably within therange of 0.0001 to 1.0 per cent by weight, especially 0.0001 to 0.01 percent by weight. In a primary composition, the amount of activeingredient can vary widely and can be, for example, from 5 to 95 percentby weight of the composition.

[0084] In use a compound of the invention is generally applied to seeds,plants or their habitat. Thus, the compound can be applied directly tothe soil before, at or after drilling so that the presence of activecompound in the soil can control the growth of fungi which may attackseeds. When the soil is treated directly the active compound can beapplied in any manner which allows it to be intimately mixed with thesoil such as by spraying, by broadcasting a solid form of granules, orby applying the active ingredient at the same time as drilling byinserting it in the same drill as the seeds. A suitable application rateis within the range of from 5 to 1000 g per hectare, more preferablyfrom 10 to 500 g per hectare.

[0085] Alternatively the active compound can be applied directly to theplant by, for example, spraying or dusting either at the time when thefungus has begun to appear on the plant or before the appearance offungus as a protective measure. In both such cases the preferred mode ofapplication is by foliar spraying. It is generally important to obtaingood control of fungi in the early stages of plant growth, as this isthe time when the plant can be most severely damaged. The spray or dustcan conveniently contain a pre- or post-emergence herbicide if this isthought necessary. Sometimes, it is practicable to treat the roots,bulbs, tubers or other vegetative propagule of a plant before or duringplanting, for example, by dipping the roots in a suitable liquid orsolid composition. When the active compound is applied directly to theplant a suitable rate of application is from 0.025 to 5 kg per hectare,preferably from 0.05 to 1 kg per hectare.

[0086] In addition, the compounds of the invention can be applied toharvested fruits, vegetables or seeds to prevent infection duringstorage.

[0087] In addition, the compounds of the invention can be applied toplants or parts thereof which have been genetically modified to exhibita trait such as fungal and/or herbicidal resistance.

[0088] In addition the compounds of the invention can be used to treatfungal infestations in timber and in public health applications. Alsothe compounds of the invention can be used to treat fungal infestationsin domestic and farm animals.

[0089] Compounds of the invention may be prepared, in known manner, in avariety of ways.

[0090] Compounds of general formula I may be prepared from compounds ofgeneral formula II according to Scheme 1. Such reactant can be obtainedfrom commercial suppliers or prepared by methods apparent to the skilledin the art. As a general manner, all starting materials used for thepreparation of the compounds of the invention are either commerciallyavailable or can be prepared by well-known method from the skilled inthe art. Such methods can for example be found in the literature, inpatents, in the “Chemical Abstracts”, in electronic databases or on theInternet.

[0091] The following reaction conditions may be used to effectconversion:

[0092] a) when R¹ is hydrogen, by reaction with H(C═O)NHR² in thepresence of POC1₃ or SOC1₂.

[0093] b) reaction with EtOCH═NR¹⁰ or EtSCH═NR¹⁰ where R¹⁰ is a groupsuch as alkyl or —CN.

[0094] c) in addition when R¹⁰ is cyano, compounds of general formula Ican be converted into other groups as defined for R² by heating in thepresence of a tertiary amine.

[0095] Such reactions are well known from the one skilled in the art andcan be conducted for example according general references such as J.March, Advanced Organic Chemistry, IV edition, pages 1276 sqq.

[0096] Compounds of general formula II may be prepared from compounds ofgeneral formula III by removal of a suitable protecting group fromnitrogen, for example, the benzyloxycarbonyl group as shown in Scheme 2.Preferred reaction conditions are heating a solution of compound III in80% dioxan with 20% 2N aqueous HC1. Other standard methods will beapparent to the chemist skilled in the art.

[0097] Compounds of general formula III may be prepared from compoundsof general formula IV according to Scheme 3. The following reactionconditions may be used to effect this conversion:

[0098] a) treatment of compounds of formula IV with a strong base, forexample sodium hydride, followed by an alkylating agent, for exampleR′—Br or R′—I where R′represents alkyl;

[0099] b) treatment with an acyl chloride in the presence of a mild basesuch as pyridine or triethylamine. Other standard methods will beapparent to the chemist skilled in the art.

[0100] Compounds of general formula IV may be prepared from compounds ofgeneral formula V according to Scheme 4. Preferred reaction conditionscomprise reaction with (^(t)BuOC═O)₂O at ambient temperature inalcoholic solvents. Alternative protection groups to ^(t)BuOC═O will beapparent to the chemist skilled in the art for these series ofreactions.

[0101] Compounds of general formula V may be prepared by reduction ofthe nitro group in compounds of formula VI according to reaction Scheme5. Preferred reaction conditions comprise reaction with stannouschloride in concentrated hydrochloric acid.

[0102] Compounds of formula Va, i.e. compounds of general formula Vwhere A is a direct bond, may be prepared according to reaction Scheme6, where X^(V) is a leaving group.

[0103] Compounds of formula Vb, i.e. compounds of general formula Vwhere R⁴ is halogen, may be prepared according to Scheme 7 where X^(T)represents halogen. When R⁴ is bromine preferred reaction conditionscomprise stirring with bromine in a suitable solvent.

[0104] Compounds of formula Vc, i.e. compounds of general formula Vwhere A is NHC(═O)—; compounds of formula Vd, i.e. compounds of formulaV where A is a direct bond and R⁶ is optionally substituted phthalimido,where the curved line connecting the 3 and 4 positions of thephthalimido group represents the optionally substituted carbocyclicring; and compounds of formula Ve, i.e. compounds of general formula Vwhere A is a direct bond and R⁶ is pyrrolyl, optionally substituted atthe 2 and 5 positions by one or more groups R which may be the same ordifferent; may be prepared from compounds of formula VII according tomethodology shown in reaction Scheme 8. For certain compounds of formulaVII, protection/deprotection of the amino group ortho to R⁴ may berequired to improve yields.

[0105] Compounds of formula VIa, i.e. compounds of general formula VIwhere A is a group A^(Z), may be prepared by reacting compounds offormula VIII with compounds of formula IX according to reaction Scheme9. A^(Z) is a group which, in compound VIII, forms an anion under basicconditions. AZ is alternatively a basic primary or secondary nitrogenatom. X^(Z) is a leaving group, preferably halogen. When A^(Z) isoxygen, preferred reaction conditions comprise treating VIII with sodiumhydride followed by addition of IX. When A^(Z) is sulphur preferredreaction conditions comprise reacting VIII with IX in the presence of atertiary amine base such as ethyldiisopropylamine. When A^(Z) is —CHR⁷—,preferred reaction conditions comprise treating VIII with potassiumtert-butoxide in dimethylformamide at low temperature. When A^(Z) is abasic nitrogen atom, no base is required.

[0106] Compounds of formula VIb, i.e. compounds of general formula VIwhere A is a group A^(W), may be prepared by reacting compounds offormula X with compounds of formula XI according to reaction scheme 10.A^(W) is a group which, in compound X, forms an anion under basicconditions. X^(W) is a leaving group, preferably halogen. Preferredbasic conditions comprise reaction of X with potassium carbonate orsodium hydride followed by addition of XI.

[0107] Compounds of formula VIc, i.e. compounds of general formula VIwhere A is O, may be prepared by reacting compounds of formula XII withboronic acids of formula XIII according to Scheme 11. Preferred reactionconditions comprise reaction with copper acetate and triethylamine.

[0108] Compounds of formula VId, i.e. compounds of formula VI where A isa direct bond may be prepared according to reaction Scheme 12 fromcompounds of formula XIV where X^(Z) is a leaving group, preferablyhalogen.

[0109] Compounds of formula VI where A is a direct bond and R⁶ is aheterocyclyl can be prepared using a variety of methods known to askilled chemist (for example see “Comprehensive Heterocyclic Chemistry”,Vols 1-7, A. R. Katritzky and C. W. Rees). By way of example, routes tocompounds of formula VI containing a 1,2,4-oxadiazol-3-yl group(compound VIe) and a 1,3,4-oxadiazol-2-yl group (compound VIf) are shownin Schemes 13 and 14.

[0110] Other methods will be apparent to the chemist skilled in the art,as will be methods for preparing starting materials and intermediates.

[0111] In addition, compounds of the invention may be prepared usingcombinatorial chemistry methodology.

[0112] The invention is illustrated in the following Examples.Structures of isolated, novel compounds were confirmed by N.M.R., massspectrometry and/or other appropriate analyses. Proton N.M.R. spectra (¹H N.M.R.) were determined in deuterochloroform and chemical shifts (6)are quoted in parts per million downfield of tetramethylsilane.

EXAMPLE 1 Preparation of N-methyl-N′-methyl-[4-(3-tert-butylphenoxy)-2,5-xylyl]formamidine

[0113] Compound 2, see table 1 below

[0114] To the product from stage a) (1.0 g) and N-methylformamidine(0.25 g) in orthodichlorobenzene (5 ml) was added thionyl chloride (0.46g). The solution was heated at 65° C. for 3 hours and allowed to cool toambient temperature. Triethylamine was added, followed by water and theproduct was extracted into ethyl acetate. The organic phase was washedwith sodium hydrogenocarbonate solution and evaporated to dryness. Thecrude product was purified by flash chromatography to afford the titlecompound as a pale yellow oil (0.60 g).

[0115] Preparation of starting materials

[0116] Stage a): Preparation ofN-methyl-[4-(3-tert-butylphenoxy)-2,5-xylyl]aniline

[0117] The product from stage b) (4.8 g) was dissolved in dioxan (50 ml)and 2N hydrochloric acid (15 ml), and the solution was heated at refluxfor one hour. After cooling the mixture was poured into water andneutralised with 2N sodium hydroxide solution. The product was extractedinto ethyl acetate, washed once with water, and concentrated to a brownoil which crystallised on standing to afford the title compound (3.15g).

[0118] Stage b): Preparation ofN-methyl-N-tert-butoxycarbonyl-[4-(3-tert-butyl-phenoxy)-2,5-xylyl]aniline

[0119] Sodium hydride (0.54 g, 60% in mineral oil) was added to asolution of the product from stage c) (4.7 g) in dimethylformamide (70ml) at 0°C. and the mixture was stirred at this temperature for onehour. Methyl iodide (1.9 g) was then added dropwise and the solution wasstirred for 4 hours.

[0120] The reaction mixture was poured into water (500 ml) and extractedwith ether. The combined ether extracts were washed once with water,brine, dried over magnesium sulphate, filtered and concentrated todryness, to afford the title compound (4.85 g) as a brown oil.

[0121] Stage c): Preparation ofN-tert-butoxycarbonyl-[4-(3-tert-butylphenoxy)-2, 5-xylyl]aniline

[0122] To a solution of the product from stage d) (8. lg) andtriethylamine(4.5 g) in methanol (100 ml) was added dropwise a solutionof tert-butoxycarbonyl anhydride (13.7 g) in methanol (20 ml). Thesolution was stirred at ambient temperature for one hour and evaporatedto dryness. Water was added and the product was extracted into ethylacetate, which was washed once with water, dried over magnesiumsulphate, filtered and concentrated to a brown oil. The title compoundwas purified by flash chromatography to afford a colourless solid (9.0g)

[0123] Stage d): Preparation of 4-(3-tert-butylphenoxy)-2,5-xylidine

[0124] To a stirred mixture of stannous chloride (10.8 g) inconcentrated hydrochloric acid (24 ml) and ethanol (50 ml) was added theproduct from stage e) below (2.46 g) and the mixture was heated at 75°C. for 2 hours. On cooling potassium hydroxide solution was added slowlywith cooling. The mixture was extracted with diethyl ether (×3) and thecombined extracts were washed with brine, dried over magnesium sulphate,filtered and evaporated to dryness to give a crude residue which waspurified by silica gel chromatography eluting with light petroleum (b.p.60-80° C.)/ethyl acetate (3:1) to give the title product.

[0125] Stage e): Preparation of 2-nitro-5-(3-tert-butylphenoxy)-p-xylene

[0126] To a suspension of sodium hydride (0.4 g of 60% in oil) in dryN-methylpyrroli-dinone (10 ml) was slowly added 3-tert-butylphenol (1.62g). When effervescence had ceased, 3-chloro-6-nitro-p-xylene (1.85 g)was added and the mixture stirred at 120-40° C. for 5 hours. On cooling,the mixture was poured into water and the mixture extracted with diethylether (×3). The combined ether extracts were dried over magnesiumsulphate, filtered and evaporated to give the title compound as a solid.

[0127] The following compounds of formula Ia (see Table 1), i.e.compounds of general formula I where —A—R⁶ is para to the amidinemoiety, may be prepared by methods analogous to those of Example 1.TABLE 1 (Ia)

Cmpd R1 R2 R3 R4 R5 A R6 1 H CN Me Me 5-Me O m-t-Buphenyl 2 H Me Me Me5-Me O m-t-Buphenyl 3 H Me n- Me 5-Me O m-t-Buphenyl Propyl 4 H Me Et Me5-Me O m-t-Buphenyl 5 H Et Me Me 5-Me O m-t-Buphenyl 6 H Et n- Me 5-Me Om-t-Buphenyl Propoyl 7 H CN Me Me 5-Me O m-trifluoro- methyl-p-chlorophenyl 8 H CN Et Me 5-Me O m-trifluoro- methyl- p-chlorophenyl 9H CN Acetyl Me 5-Me O m-trifluoro- methyl- p-chlorophenyl 10 H4-fluorobenzyl Et Me 5-Me O m-trifluoro- methyl- p-chlorophenyl

[0128] TABLE 2 Analytical data MS Cmpd NMR (CDCl₃) (M + 1) 1 382 2 1.25(s, 9H, C(CH3)3); 2.10(s, 3H, ArCH3);  2.15(s, 3H, ArCH3); 3.10(s,3H, N(CH3));  3.15(s, 3H, N(CH3)) 3  0.80(t, 3H, CH2CH3); 1.20(s, 9H,C(CH3)3);  1.50(q, 2H, CH2CH2CH3); 2.10(s, 3H, ArCH3);  2.15(s, 3H,ArCH3); 3.10(s, 3H, N(CH3));  3.50(m, 2H, N(CH2CH2) 4  1.00(t, 3H,CH2CH3); 1.20(s, 9H, C(CH3)3);  2.10(s, 3H, ArCH3); 2.15(s, 3H, ArCH3); 3.10(s, 3H, NCH3); 3.60(q, 2H, NCH2CH3) 5  1.10(t, 3H, CH2CH3); 1.25(s,9H, C(CH3)3);  2.10(s, 3H, ArCH3); 2.15(s, 3H, ArCH3);  3.10(s, 3H,NCH3); 3.30(q, 2H, NCH2) 6  0.80(t, 3H, CH2CH2CH3); 1.05(t, 3H, CH2CH3); 1.20(s, 9H, C(CH3)3); 1.50(m, 2H, CH2CH2CH3);  2.10(s, 3H, ArCH3);2.15(s, 3H, ArCH3);  3.20(q, 2H, CH2CH3); 3.40(m, 2H, CH2CH2CH3) 8 1.2(t, 3H, NCH2CH3); 2.15(s, 3H, ArCH3);  2.2(s, 3H, ArCH3); 3.8(q, 2H,NCH2CH3) 9 336 10  479

Test Examples

[0129] Compounds were assessed for activity against one or more of thefollowing Phytopathogenic diseases:

[0130]Erysiphe graminis f. sp. tritici: wheat powdery mildew

[0131]Puccinia recondita: wheat brown rust

[0132]Septoria nodorum: wheat septoria nodorum

[0133]Septoria tritici: wheat septoria tritici

[0134]Pyrenophora teres: barley net blotch

[0135] Aqueous solutions or dispersions of the compounds of theinvention at the desired concentration, including one or more wettingagents, were applied by spray or by drenching the stem base of the testplants, as appropriate. After a given time, plants or plant parts wereinoculated with appropriate test pathogens and kept under controlledenvironmental conditions suitable for maintaining plant growth anddevelopment of the disease. After an appropriate time, the degree ofinfection of the affected part of the plant was visually estimated. At aconcentration of 500 ppm (w/v) or less, the following compounds presenta control of at least 65% on the specified fungal diseases versusnon-treated test.

[0136]Erysiphe graminis f. sp. tritici: 5, 10

[0137]Leptosphaeria nodorum: 10

[0138]Pyrenophora teres: 10

1. A compound of general formula I and salts thereof as fungicides

wherein R¹ is chosen from among alkyl, alkenyl, alkynyl, acyl,carbocyclyl, heterocyclyl, each of which may be substituted, cyano andhydrogen; R² and R³, which may be the same or different, are any groupdefined for R¹; cyano; acyl; —OR^(a), —NR^(a)R^(b) or —SR^(a), whereR^(a) and R^(b), which may be the same or different, are chosen fromalkyl, alkenyl, alkynyl, acyl, carbocyclyl, heterocyclyl, each of whichmay be substituted, and cyano; or R² and R³, or R² and R¹, together withtheir interconnecting atoms may form a ring, which may be substituted;R⁴ is chosen from among alkyl, alkenyl, alkynyl, carbocyclyl,heterocyclyl, each of which may be substituted; hydroxy; mercapto;azido; nitro; halogen; cyano; acyl; optionally substituted amino;cyanato; thiocyanato; —SF₅; —OR^(a); —SR^(a) and —Si(R^(a))₃, whereR^(a) is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each ofwhich may be substituted; m is 0 to 3; when present R⁵, which may be thesame or different to any other R⁵, is any group defined for R⁴; R⁶ isoptionally substituted carbo— or hetero—cyclyl; and A is a direct bond,—O—, —S(O)_(n)—, —NR⁹—, —CR⁷═CR⁷—, —C≡C—, —A¹—, —A¹—A¹—, —O—(A¹)_(k)—O—,—O—(A¹)_(k)—, —A³—, —A⁴—, —A¹O—, —A¹S(O)_(n)—, —A²—, —OA²—, —NR⁹A²—,—OA²—A¹—, —OA²—C(R⁷)═C(R⁸)—, —S(O)_(n)A¹—, —A¹—A⁴—,—A¹—A⁴—C(R⁸)═N—N═CR⁸—, —A¹—A⁴—C(R⁸)═N—X²—X³—, —A¹—A⁴—A³—, —A¹—A⁴—N(R⁹)—,—A¹—A⁴—X—CH₂—, —A¹—A⁴—A¹—, —A¹—A⁴—CH₂X—, —A¹—A⁴—C(R⁸)═N—X²—X³—X¹—,—A¹—X—C(R⁸)═N—, —A¹—X—C(R⁸)═N—N═CR⁸—, —A¹—X—C(R⁸)═N—N(R⁹)—,—A¹—X—A²—X¹—, —A¹—O—A³—, —A¹—O—C(R⁷)═C(R⁸)—, —A¹—O—N(R⁹)—A²—N(R⁹)—,—A¹—O—N(R⁹)—A²—, —A¹—N(R⁹)—A²—N(R⁹)—, —A¹—N(R⁹)—A²—, —A¹—N(R⁹)—N═C(R⁸)—,—A³—A¹—, —A⁴—A³—, —A²—NR⁹, —A¹—A²—X¹—, —A¹—A¹—A²—X¹—, —O—A²—N(R⁹)—A²—,—CR⁷═CR⁷═CR⁷—A²—X¹—, —C≡—C—A²—X¹—, —N═C(R⁸)—A²—X¹—, —C(R⁸)═N—N═C(R⁸)—,—C(R⁸)═N—N(R⁹)—, —(CH₂)₂—O—N═C(R⁸)—ou—X—A²—N(R⁹)— where: —n is 0, 1 or2, —k is 1 to 9, —A¹is —CHR⁷—, —A² is —C(═X)—, —A³ is —C(R⁸)═N—O—, —A⁴is —O—N═C(R⁸)—, —X is O or S, —X¹ is O, S, NR⁹ or a direct bond, —X² isO, NR⁹ or a direct bond, —X³ is hydrogen, —C(═O)—, —SO₂— or a directbond, —R⁷, which may be the same or different to any other R⁷, is alkyl,alkenyl, alkynyl, cyano, acyl, hydroxy, alkoxy, haloalkoxy, alkylthio,cycloalkyl or phenyl, each of which may be substituted; or is hydrogenor halogen; —R⁸, which may be the same or different to any other R⁸, isalkyl, alkenyl, alkynyl, alkoxy, alkylthio, carbo- or hetero-cyclyl,each of which may be substituted; or is hydrogen; —R⁹, which may be thesame or different to any other R⁹, is optionally substituted alkyl,optionally substituted carbo- or hetero-cyclyl, hydrogen or acyl; or twoR⁹ groups on A, together with the connecting atoms, form a 5 to 7membered ring; where the moiety depicted on the right side of linkage Ais attached to R⁶; or —A—R⁶ and R⁵ together with benzene ring M form anoptionally substituted fused ring system.
 2. A compound according toclaim 1 wherein R¹ is alkyl, alkenyl, alkynyl or acyl, each of which maybe substituted by alkoxy, haloalkoxy, alkylthio, halogen or optionallysubstituted phenyl; or is cyano or hydrogen.
 3. A compound according toclaim 2 wherein R¹ is alkyl, alkenyl or alkynyl, each of which may besubstituted by alkoxy, haloalkoxy, alkylthio, halogen or phenyloptionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy oralkylthio, each containing 1 to 5 carbon atoms, or halogen, or ishydrogen.
 4. A compound according to any preceding claim wherein R¹ isC₁-C₁₀ alkyl or hydrogen.
 5. A compound according to any preceding claimwherein R¹ is methyl or hydrogen.
 6. A compound according to anypreceding claim wherein R² and R³, which may be the same or different,are alkyl, alkenyl or alkynyl, each of which may be substituted byalkoxy, haloalkoxy, alkylthio, halogen or optionally substituted phenyl,or are hydrogen or alkylcarbonyl.
 7. A compound according to anypreceding claim wherein R² and R³, which may be the same or different,are alkyl, alkenyl or alkynyl, each of which may be substituted byalkoxy, haloalkoxy, alkylthio, halogen or phenyl optionally substitutedby alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio, each containing 1to 5 carbon atoms, or by halogen, or are hydrogen or alkylcarbonyl.
 8. Acompound according to any preceding claim wherein R² and R³, which maybe the same or different, are C₁-C₁₀ alkyl or hydrogen.
 9. A compoundaccording to any preceding claim wherein R² and R³, which may be thesame or different, are methyl or hydrogen.
 10. A compound according toany preceding claim wherein R⁴ is alkyl, alkenyl, or alkynyl, each ofwhich may be substituted by alkoxy, haloalkoxy, alkylthio, halogen oroptionally substituted phenyl; or is hydroxy; halogen; cyano; acyl;alkoxy; haloalkoxy; or alkylthio.
 11. A compound according to anypreceding claim wherein R⁴ is alkyl, alkenyl, or alkynyl, each of whichmay be substituted by alkoxy, haloalkoxy, alkylthio, halogen or phenyloptionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy oralkylthio, each containing 1 to 5 carbon atoms, or halogen; or ishydroxy; halogen; cyano; acyl; alkoxy; haloalkoxy; or alkylthio.
 12. Acompound according to any preceding claim wherein R⁴ is alkyl, alkenyl,or alkynyl, each of which may be substituted by alkoxy, haloalkoxy,alkylthio, halogen or optionally substituted phenyl; or is hydroxy;halogen; cyano; —C(═O)R^(C), —C(═S)R^(c) or —S(O)_(p)R^(c), where R^(c)is alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, amino,monoalkylamino, dialkylamino or phenyl optionally substituted by alkyl,haloalkyl, alkoxy, haloalkoxy, phenyloxy, phenylthio, carbocyclyl,heterocyclyl or alkylthio; alkoxy; haloalkoxy; or alkylthio.
 13. Acompound according to any preceding claim wherein R⁴ is C₁-C₁₀ alkyl orhalogen.
 14. A compound according to any preceding claim wherein R⁴ ismethyl or ethyl or halogen.
 15. A compound according to any precedingclaim wherein m is 0 or
 1. 16. A compound according to any precedingclaim wherein, when present, R⁵ is a group defined for R⁴ in either ofclaims 10 to
 14. 17. A compound according to any preceding claimwherein, when present, R⁵ is attached at the 5 position of ring M.
 18. Acompound according to any preceding claim wherein A is a direct bond,—O—, —S(O)_(n)A¹—, —O(A¹)_(k)—, —S(O)_(n)—, —NR⁹A²—, —A²—, —OA²—,—OA²—A¹—, —NR⁹— or —O(A¹)_(k)O—.
 19. A compound according to anypreceding claim wherein A is a direct bond, —O—, —S—, —NR⁹—, —CHR⁷— or—O—CHR⁷—.
 20. A compound according to any preceding claim wherein A is adirect bond or —O—
 21. A compound according to any preceding claimwherein, when present, R⁹ is alkyl, alkenyl, or alkynyl, each of whichmay be substituted by alkoxy, haloalkoxy, alkylthio, halogen oroptionally substituted phenyl; or is hydrogen.
 22. A compound accordingto any preceding claim wherein, when present, R⁹ is alkyl, alkenyl, oralkynyl, each of which may be substituted by alkoxy, haloalkoxy,alkylthio, halogen or phenyl optionally substituted by alkyl, haloalkyl,alkoxy, haloalkoxy or alkylthio, each containing 1 to 5 carbon atoms, orhalogen; or is hydrogen.
 23. A compound according to any preceding claimwherein, when present, R⁹ is C₁-C₁₀ alkyl or hydrogen.
 24. A compoundaccording to any preceding claim wherein, when present, R⁷ is alkyl,alkenyl, or alkynyl, each of which may be substituted by alkoxy,haloalkoxy, alkylthio, halogen or optionally substituted phenyl; or ishydroxy; halogen; cyano; acyl; alkoxy; haloalkoxy; alkylthio; orhydrogen.
 25. A compound according to any preceding claim wherein, whenpresent, R⁷ is alkyl, alkenyl, or alkynyl, each of which may besubstituted by alkoxy, haloalkoxy, alkylthio, halogen or phenyloptionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy oralkylthio, each containing 1 to 5 carbon atoms, or by halogen; or ishydroxy; halogen; cyano; acyl; alkoxy; haloalkoxy; alkylthio; orhydrogen.
 26. A compound according to any preceding claim wherein, whenpresent, R⁷ is C₁-C₁₀ alkyl or hydrogen.
 27. A compound according to anypreceding claim wherein A is attached to the 4 position of benzene ringM.
 28. A compound according to any preceding claim wherein R⁶ isoptionally substituted aromatic heterocyclyl.
 29. A compound accordingto any preceding claim wherein R⁶ is optionally substituted thiazolyl,isothiazolyl, thiadiazolyl, pyridyl or pyrimidinyl.
 30. A compoundaccording to any preceding claim wherein R⁶ is optionally substituted1,2,4-thiadiazolyl.
 31. A compound according to any preceding claimwherein when substituted, R⁶ may be substituted by one or moresubstituents, which may be the same or different, and may be selectedfrom the list: alkyl, alkenyl, alkynyl, carbo- or heterocyclyl, each ofwhich may be substituted; hydroxy; mercapto; azido; nitro; halogen;cyano; acyl; optionally substituted amino; cyanato; thiocyanato; —SF₅;—OR^(a); —SR^(a) and —Si(R^(a))₃, where R^(a) is alkyl, alkenyl,alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted.32. A compound according to claim 31 wherein when substituted, R⁶ may besubstituted by one or more substituents, which may be the same ordifferent, and may be selected from the list: hydroxy; halogen; cyano;acyl; amino; alkylamino; dialkylamino; alkyl; haloalkyl; R^(a)O-alkyl;acyloxyalkyl; cyano-oxyalkyl; alkoxy; haloalkoxy; alkylthio;carbocyclyl, optionally substituted by alkyl, haloalkyl, alkoxy,haloalkoxy or alkylthio; and benzyl optionally substituted by alkyl,haloalkyl, alkoxy, haloalkoxy or alkylthio.
 33. The use of a compoundaccording to any preceding claim and salts thereof as fungicides.
 34. Afungicidal composition comprising at least one compound as claimed inany one of claims 1 to 32 in admixture with an agriculturally acceptablediluent or carrier.
 35. A method of combating fungi at a locus infestedor liable to be infested therewith, which comprises applying to thelocus a compound as claimed any one of claims 1 to 32.